EP0709426B1 - Mélange de stabiliseurs synergistiques - Google Patents

Mélange de stabiliseurs synergistiques Download PDF

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Publication number
EP0709426B1
EP0709426B1 EP19950810650 EP95810650A EP0709426B1 EP 0709426 B1 EP0709426 B1 EP 0709426B1 EP 19950810650 EP19950810650 EP 19950810650 EP 95810650 A EP95810650 A EP 95810650A EP 0709426 B1 EP0709426 B1 EP 0709426B1
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Prior art keywords
alkyl
formula
compound
independently
phenyl
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EP0709426B2 (fr
EP0709426A3 (fr
EP0709426A2 (fr
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François Gugumus
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BASF Schweiz AG
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Ciba Spezialitaetenchemie Holding AG
Ciba SC Holding AG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
    • C08K5/353—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/0273—Polyamines containing heterocyclic moieties in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
    • C08G73/0644—Poly(1,3,5)triazines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34926—Triazines also containing heterocyclic groups other than triazine groups

Definitions

  • the present invention relates to a stabilizer system containing two specific ones polymeric polyalkylpiperidine derivatives, the use of this stabilizer system for Stabilize organic material as well as with the stabilizer system mentioned Organic protected against thermal, oxidative or light-induced degradation Material.
  • Alkyl with up to 12 carbon atoms means, for example, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, octyl, 1,1,3,3-tetramethylbutyl, nonyl, decyl, undecyl or dodecyl.
  • R 1 , R 3 , R 6 and R 8 is C 1 -C 4 alkyl.
  • R 10 and R 11 are preferably C 1 -C 8 alkyl, especially n-butyl.
  • R 4 is preferably C 1 -C 10 alkyl, in particular 1,1,3,3-tetramethylbutyl.
  • One of the preferred meanings for R 5 is C 1 -C 4 alkyl, in particular methyl.
  • C 5 -C 12 cycloalkyl means, for example, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl or cyclododecyl.
  • C 5 -C 7 cycloalkyl is preferred, especially cyclohexyl.
  • Another preferred meaning of R 4 is cyclohexyl.
  • C 5 -C 12 cycloalkyl substituted by C 1 -C 4 alkyl means, for example, methylcyclohexyl or dimethylcyclohexyl.
  • Phenyl substituted by -OH and / or C 1 -C 10 -alkyl means, for example, methylphenyl, dimethylphenyl, trimethylphenyl, tert-butylphenyl or 3,5-di-tert-butyl-4-hydroxyphenyl.
  • C 7 -C 9 phenylalkyl preferably means benzyl.
  • C 7 -C 9 phenylalkyl substituted on the phenyl radical by -OH and / or C 1 -C 10 alkyl means, for example, methylbenzyl, dimethylbenzyl, trimethylbenzyl, tert-butylbenzyl or 3,5-di-tert-butyl-4-hydroxybenzyl.
  • C 7 -C 9 phenylalkyl substituted on the phenyl radical by C 1 -C 4 alkyl means, for example, methylbenzyl, dimethylbenzyl, trimethylbenzyl or tert-butylbenzyl.
  • C 3 -C 6 alkenyl examples are allyl, 2-methallyl, butenyl, pentenyl and hexenyl. Allyl is preferred.
  • R 5 as C 1 -C 8 acyl preferably denotes C 1 -C 8 alkanoyl, C 3 -C 8 alkenoyl or benzoyl. Examples are formyl, acetyl, propionyl, butyryl, pentanoyl, hexanoyl, octanoyl, benzoyl, acryloyl and crotonoyl.
  • alkylene with up to 18 carbon atoms examples include ethylene, propylene, trimethylene, tetramethylene, pentamethylene, 2,2-dimethyltrimethylene, hexamethylene, trimethylhexamethylene, octamethylene, decamethylene, undecamethylene and dodecamethylene.
  • R 2 and R 7 are preferably C 2 -C 6 alkylene.
  • R 2 and R 7 are particularly preferably hexamethylene.
  • C 5 -C 7 cycloalkylene is cyclohexylene.
  • C 1 -C 4 alkylene di (C 5 -C 7 cycloalkylene) is methylenedicyclohexylene.
  • radicals R 1 , R 2 and R 3 or the radicals R 6 , R 7 and R 8 together with the nitrogen atoms to which they are attached form a 5- to 10-membered heterocyclic ring, they are, for example A 6-membered heterocyclic ring is preferred.
  • radicals R 9 and R 10 together with the nitrogen atom to which they are attached form a 5- to 10-membered heterocyclic ring, it is, for example, 1-pyrrolidyl, piperidino, morpholino, 1-piperazinyl, 4-methyl -1-piperazinyl, 1-hexahydroazepinyl, 5,5,7-trimethyl-1-homopiperazinyl or 4,5,5,7-tetramethyl-1-homopiperazinyl.
  • the group means particularly preferably morpholino.
  • R 1 , R 3 , R 6 and R 8 are particularly preferably a group of the formula II.
  • the compounds described as components a) to d) are essentially known (some of them are commercially available) and can be prepared using known methods, for example how in US-A-4 086 204, US-A-4 331 586, US-A-4 477 615, Chemical Abstracts-CAS No. 136 504-96-6 and US-A-4,340,534.
  • Component c) can, for example, in analogy to known processes Reaction of a polyamine of formula IVa with cyanuric acid chloride in one molar ratio of 1: 2 to 1: 4 in the presence of anhydrous lithium, sodium or Potassium carbonate in an organic solvent such as 1,2-dichloroethane, toluene, Xylene, benzene, dioxane or tert-amyl alcohol at a temperature of -20 ° C to + 10 ° C, preferably-10 ° C to + 10 ° C, especially 0 ° C to + 10 ° C, for 2 to 8 hours and subsequent reaction of the product obtained with a 2,2,6,6-tetramethyl-4-piperidylamine of the formula IVb can be prepared.
  • an organic solvent such as 1,2-dichloroethane, toluene, Xylene, benzene, dioxane or tert-amyl alcohol
  • the molar Ratio of 2,2,6,6-tetramethyl-4-piperidylamine to the polyamine of the formula used For example, IVa is 4: 1 to 8: 1.
  • the amount of 2,2,6,6-tetramethyl-4-piperidylamine can be added all at once or in several portions every few hours become.
  • the ratio of polyamine of the formula is preferably IVa: cyanuric acid chloride: 2,2,6,6-tetramethyl-4-piperidylamine of the formula IVb 1: 3: 5 to 1: 3: 6.
  • component c) can be represented, for example, by a compound of the formula IV-1, IV-2 or IV-3. It can also be a mixture of these three compounds.
  • n 3 preferably denotes 1 to 20, with 1 being excluded.
  • Component a) is preferably ®CHIMASSORB 944 or ®DASTIB 1082, as Component b) ®CYASORB UV 3346, as component c) ®UVASORB HA 88 and as Component d) ®HOSTAVIN N 30 used.
  • the compound of formula VI means in particular ®TINUVIN 622 and can be used for Example prepared in analogy to the methods described in US-A-4,233,412 become.
  • the compounds of the formulas Va and Vb can be obtained together as a mixture, where the ratio of Va: Vb e.g. Can be 20: 1 to 1:20 or 1:10 to 10: 1.
  • X is a halogen, it is advantageous to replace it, for example, with —OH or an amino group after the reaction has ended.
  • amino groups are: pyrrolidin-1-yl, morpholino, -NH 2 , -N (C 1 -C 8 alkyl) 2 and -NR (C 1 -C 8 alkyl), in which R is hydrogen or a group of formula II.
  • the end group which is bonded to the triazine radical is, for example, Cl or a group and the end group attached to the amino group, for example hydrogen or a group
  • the end group attached to the nitrogen e.g. B. is hydrogen and the end group which is bonded to the 2-hydroxypropylene radical can, for. B. a group his.
  • the end group attached to the dimethylene radical is bound, e.g. B. -OH and the end group which is bonded to the oxygen, can e.g. B. be hydrogen.
  • the end groups can also represent polyether residues.
  • the compounds of the formula VI are prepared, for example, by reacting a compound of the formula where R 13 is hydrogen or methyl, with a dicarboxylic acid diester of the formula Y-OOC-R 14 -COO-Y, where Y is, for example, methyl, ethyl or propyl and R 14 has the meaning given above, is the end group which is attached to the 2,2,6,6-tetramethyl-4-oxypiperidin-1-yl radical, hydrogen or -CO-R 14 -COO-Y and the end group which is bound to the diacyl radical means -OY or
  • a stabilizer mixture containing at least one compound from component a) and at least one compound from component b) is particularly preferred.
  • a stabilizer mixture consisting of a compound of the formula I is also preferred and a compound of formula III.
  • a further preference of the invention is containing a stabilizer mixture at least one compound from component a), b) or c) and at least one Compound from component d).
  • n 1 , n 2 , n 4 and n 4 * which are the same or different, preferably mean a number from 2 to 40, in particular 2 to 25, for example 2 to 20 or 2 to 10.
  • n 3 ', n 3 ''and n 3 ''' independently of one another are in particular 2 to 4.
  • a particularly preferred embodiment of the invention is a stabilizer mixture in which the compound of the formula I or is and the compound of formula III means and n 1 , n 2 , n 4 and n 4 * independently of one another represent a number from 2 to 20.
  • Another particularly preferred embodiment of the invention is a stabilizer mixture containing the compounds and where n 1 and n 2 independently of one another represent a number from 2 to 20.
  • n 3 ', n 3 ''and n 3 ''' independently of one another are a number from 2 to 4, R 11 C 1 -C 4 alkyl and R 12 are hydrogen.
  • Component c) is particularly preferably a product obtainable by reacting a reaction of a polyamine of the formula product obtained with cyanuric acid chloride with a compound of the formula
  • Another object of the invention is therefore a composition containing a Organic sensitive to oxidative, thermal or light-induced degradation Material and a stabilizer mixture according to the invention.
  • the organic material is preferably synthetic polymers, especially those from the above groups.
  • Polyolefins are preferred and Polyethylene, polypropylene and their copolymers are particularly preferred.
  • the compounds of the stabilizer system according to the invention can be used individually or mixed together to be added to the material to be stabilized. You can the compounds for example independently in amounts of 0.01 to 4.99% are used with the condition that the total amount of the inventive Stabilizer mixture preferably 0.02 to 5%, based on the total weight of the stabilizing material.
  • the total amount of the stabilizer system according to the invention is preferably 0.05 to 3%, in particular 0.05 to 2% or 0.05 to 1%, based on the total weight of the stabilizing material.
  • the weight ratio of the two compounds of the invention Stabilizer system is preferably 20: 1 to 1:20, in particular 10: 1 to 1:10, for example 1: 5 to 5: 1.
  • the incorporation of the stabilizer mixture according to the invention or the Individual compounds in the organic material can be made by known methods, for example before or during shaping or by applying the loosened or dispersed compounds on the organic material, optionally under subsequent evaporation of the solvent.
  • the individual connections of the Stabilizer mixture according to the invention can be in the form of powder, granules or else in the form of a masterbatch, for example in a concentration of 2.5 to 25 Contains% by weight, which are added to the materials to be stabilized.
  • the compounds of the stabilizer system according to the invention be mixed with one another before incorporation into the melt (melt-blending).
  • the stabilizer system according to the invention or its compounds can before or be added during the polymerization or before crosslinking.
  • the materials stabilized in this way can be used in various forms, e.g. as foils, fibers, tapes, molding compounds, profiles or as binders for paints, Adhesives or putties.
  • the stabilized organic materials of the invention can additionally contain various conventional additives, such as:
  • Alkylated monophenols e.g. 2,6-di-tert-butyl-4-methylphenol, 2-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert- butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-iso-butylphenol, 2,6-di-cyclopentyl-4-methylphenol, 2- ( ⁇ -methylcyclohexyl) -4,6-dimethylphenol, 2,6-di-octadecyl-4-methylphenol, 2,4,6-tri-cyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, 2,6-di-nonyl-4-methylphenol, 2, 4-dimethyl-6- (1'-methyl-undec-1'-yl) phenol, 2,4-dimethyl-6- (1'-methyl-hepta
  • Alkylthiomethylphenols for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-4 -nonylphenol.
  • Hydroquinones and alkylated hydroquinones for example 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butyl-hydroquinone, 2,5-di-tert-amyl-hydroquinone, 2,6-diphenyl- 4-octadecyloxyphenol, 2,6-di-tert-butyl-hydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5- Di-tert-butyl-4-hydroxyphenyl stearate, bis (3,5-di-tert-butyl-4-hydroxyphenyl) adipate.
  • 2,6-di-tert-butyl-4-methoxyphenol 2,5-di-tert-butyl-hydroquinone, 2,5-di-tert-amyl-hydroquinone, 2,6-diphen
  • Tocopherols e.g. ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol and mixtures thereof (vitamin E).
  • Hydroxylated thiodiphenyl ethers e.g. 2,2'-thio-bis- (6-tert-butyl-4-methylphenol), 2,2'-thio-bis- (4-octylphenol), 4,4'-thio-bis- ( 6-tert-butyl-3-methylphenol), 4,4'-thio-bis- (6-tert-butyl-2-methylphenol), 4,4'-thio-bis- (3,6-di-sec. -amylphenol), 4,4'-bis (2,6-dimethyl-4-hydroxyphenyl) disulfide.
  • 2,2'-thio-bis- (6-tert-butyl-4-methylphenol 2,2'-thio-bis- (4-octylphenol), 4,4'-thio-bis- ( 6-tert-butyl-3-methylphenol), 4,4'-thio-bis- (6-tert-butyl-2-methylphenol), 4,4'-thio-bis- (3,6-di-sec
  • Alkylidene bisphenols e.g. 2,2'-methylene-bis- (6-tert-butyl-4-methylphenol), 2,2'-methylene-bis- (6-tert-butyl-4-ethylphenol), 2.2 '-Methylene-bis- [4-methyl-6- ( ⁇ -methylcyclohexyl) phenol], 2,2'-methylene-bis- (4-methyl-6-cyclohexylphenol), 2,2'-methylene-bis- (6-nonyl-4-methylphenol), 2,2'-methylene-bis- (4,6-di-tert-butylphenol), 2,2'-ethylidene-bis- (4,6-di-tert-butylphenol) ), 2,2'-ethylidene-bis- (6-tert-butyl-4-isobutylphenol), 2,2'-methylene-bis- [6- ( ⁇ -methylbenzyl) -4-nonylphenol], 2,2 ' --methylene
  • O-, N- and S-benzyl compounds for example 3,5,3 ', 5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzyl-mercaptoacetate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) amine, bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) di-thioterephthalate, bis- (3,5-di tert-butyl-4-hydroxybenzyl) sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzyl-mercaptoacetate.
  • hydroxybenzylated malonates e.g. dioctadecyl-2,2-bis (3,5-di-tert-butyl-2-hydroxybenzyl) malonate, di-octadecyl-2- (3-tert-butyl-4-hydroxy-5-methylbenzyl ) malonate, di-dodecylmercaptoethyl-2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate, di- [4- (1,1,3,3-tetramethylbutyl) phenyl ] -2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate.
  • Hydroxybenzyl aromatics e.g. 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis- (3,5-di- tert-butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) phenol.
  • Triazine compounds e.g. 2,4-bis-octylmercapto-6- (3,5-di-tert-butyl-4-hydroxy-anilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis- ( 3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis- (3,5-di-tert-butyl-4-hydroxyphenoxy) -1 , 3,5-triazine, 2,4,6-tris- (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,2,3-triazine, 1,3,5-tris- (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 1,3,
  • Benzylphosphonates e.g. dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate , Dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, Ca salt of the 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester.
  • Acylaminophenols for example 4-hydroxylauric anilide, 4-hydroxystearic anilide, N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamic acid octyl ester.
  • esters of ⁇ - (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with mono- or polyhydric alcohols such as with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol , Ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxalic acid diamide, 3-thiaundecanol, 3-thiapentadiolanol, trimethylhexane Trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo- [2.2.2] octane.
  • esters of ⁇ - (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid with mono- or polyhydric alcohols such as with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol , Ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxy) ethyl isocyanurate, N, N'-bis (hydroxyethyl) oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, tri -methylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo- [2.2.2] o
  • esters of ⁇ - (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid with mono- or polyhydric alcohols such as with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1 , 2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxy) ethyl isocyanurate, N, N'-bis (hydroxyethyl) oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylolpropanediol, trimethylolpropanediol -Hydroxymethyl-1-phospha-2,6,7-trioxabicyclo-
  • esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with mono- or polyhydric alcohols such as with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2 Propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxy) ethyl isocyanurate, N, N'-bis (hydroxyethyl) oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexethylpanediol, trimethylhexanediol -1-phospha-2,6,7-trioxabicyclo- [2.2.2] octane.
  • 2.2.2-hydroxybenzophenones such as the 4-hydroxy-, 4-methoxy-, 4-octoxy-, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy-, 4,2 ', 4'-trihydroxy-, 2'-hydroxy-4,4'-dimethoxy derivative.
  • Esters of optionally substituted benzoic acids such as, for example, 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis- (4-tert-butylbenzoyl) resorcinol, benzoylresorcinol, 3,5-di-tert-butyl-4- 2,4-di-tert-butylphenyl hydroxybenzoate, 3,5-di-tert-butyl-4-hydroxybenzoic acid, hexadecyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid, octadecyl ester, 3,5-di-tert- 2-methyl-4,6-di-tert-butylphenyl butyl-4-hydroxybenzoate.
  • Acrylates such as, for example, ⁇ -cyano- ⁇ , ⁇ -diphenylacrylic acid ethyl or isooctyl ester, ⁇ -carbomethoxy-cinnamic acid methyl ester, ⁇ -cyano- ⁇ -methyl-p-methoxy-cinnamic acid methyl ester or -butyl ester, ⁇ -carbomethoxy-p- methoxy cinnamic acid methyl ester, N- ( ⁇ -carbomethoxy- ⁇ -cyanovinyl) -2-methyl-indoline.
  • Nickel compounds such as nickel complexes of 2,2'-thio-bis- [4, (1,1,3,3-tetramethylbutyl) phenol], such as the 1: 1 or the 1: 2 complex, optionally with additional ones
  • Ligands such as n-butylamine, triethanolamine or N-cyclohexyl-diethanolamine, nickel dibutyldithiocarbamate, nickel salts of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid monoalkyl esters, such as of methyl or ethyl ester, nickel complexes of ketoximes, such as of 2- Hydroxy-4-methyl-phenyl-undecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxy-pyrazole, optionally with additional ligands.
  • Ligands such as n-butylamine, triethanolamine or N-cyclohexyl-diethanolamine, nickel dibutyldithio
  • Sterically hindered amines such as bis (2,2,6,6-tetramethyl-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-piperidyl) succinate, bis (1,2,2 , 6,6-pentamethylpiperidyl) sebacate, n-butyl-3,5-di-tert-butyl-4-hydroxybenzyl-malonic acid bis (1,2, 2,6,6-pentamethylpiperidyl) ester, condensation product from 1 -Hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, tris (2,2,6,6-tetramethyl-4-piperidyl) -nitrilotriacetate, tetrakis (2,2,6,6- tetramethyl-4-piperidyl) -1,2,3,4-butanetetraoate, 1,1 '- (1,2-ethanediyl) bis- (3,3,5,
  • Oxalic acid diamides such as 4,4'-di-octyloxy-oxanilide, 2,2'-diethoxy-oxanilide, 2,2'-di-octyloxy-5,5'-di-tert-butyl-oxanilide, 2,2 '-Di-dodecyloxy-5,5'di-tert-butyl-oxanilide,2-ethoxy-2'-ethyl-oxanilide, N, N'-bis (3-dimethylaminopropyl) oxalamide, 2-ethoxy-5-tert -butyl-2'-ethyloxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butyl-oxanilide, mixtures of o- and p-methoxy- and of o- and p-ethoxy -di-substituted
  • Metal deactivators such as N, N'-diphenyloxalic acid diamide, N-salicylal-N'-salicyloyl hydrazine, N, N'-bis (salicyloyl) hydrazine, N, N'-bis (3,5-di-tert -butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1,2,4-triazole, bis (benzylidene) oxalic acid dihydrazide, oxanilide, isophthalic acid dihydrazide, sebacic acid bis-phenylhydrazide, N, N'-diacetyl adipic acid dihydrazide, N, N'-bis-salicyloyl-oxalic acid dihydrazide, N, N'-bis-salicyloyl-thiopropionic acid dihydrazide.
  • phosphites and phosphonites such as triphenyl phosphite, diphenylalkyl phosphites , phenyl dialkyl phosphites , tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris (2,4-di-tert-butylphenylphosphite) phosphite Bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis-isodecyloxy-pentaerythritol diphosphite, bis (2,4-di -tet-butyl
  • Peroxide-destroying compounds such as esters of ⁇ -thio-dipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl ester, mercaptobenzimidazole, the zinc salt of 2-mercaptobenzimidazole, zinc dibutyl dithiocarbamate, dioctadecyl disulfide, penta ⁇ -dodecylmercapto) propionate.
  • esters of ⁇ -thio-dipropionic acid for example the lauryl, stearyl, myristyl or tridecyl ester, mercaptobenzimidazole, the zinc salt of 2-mercaptobenzimidazole, zinc dibutyl dithiocarbamate, dioctadecyl disulfide, penta ⁇ -dodecylmercapto) propionate.
  • Polyamide stabilizers such as copper salts in combination with iodides and / or phosphorus compounds and salts of divalent manganese.
  • Basic co-stabilizers such as melamine, polyvinylpyrrolidone, dicyandiamide, tri-allyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali and alkaline earth metal salts of higher fatty acids, for example Ca stearate, Zn stearate, Mg -Behenate, Mg stearate, Na ricinoleate, K palmitate, antimony catecholate or tin catecholate.
  • Basic co-stabilizers such as melamine, polyvinylpyrrolidone, dicyandiamide, tri-allyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali and alkaline earth metal salts of higher fatty acids, for example Ca stearate, Zn stearate, Mg -Behenate, Mg stearate, Na
  • Nucleating agents such as 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid.
  • Fillers and reinforcing agents such as calcium carbonate, silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite.
  • additives such as plasticizers, lubricants, emulsifiers, pigments, optical brighteners, flame retardants, antistatic agents, blowing agents.
  • the weight ratio of the stabilizer mixture according to the invention conventional additives can be, for example, 1: 0.5 to 1: 5.
  • Another object of the invention is the use of the inventive Stabilizer mixture for stabilizing organic material against oxidative, thermal or light-induced degradation.
  • the organic stabilized with the inventive stabilizer system Materials are not only characterized by significantly improved light resistance but also by an extraordinarily improved thermal resistance.
  • n 1 is 4.5.
  • n 1 The mean of n 1 is 5.1.
  • n 2 is 3.5.
  • the granules obtained are in a Laboratory melt spinning system at a maximum temperature of 270 ° C and one Speed of 600 m / min spun into a 12.1 decitex multifilament. This is drawn and twisted with a draw twisting machine. The stretch ratio is 1: 3.2, so that finally multifilaments of 3.9 decitex are obtained.
  • This Multifilaments are mounted on white cardboard, 20 minutes in an oven at 120 ° C treated (simulation of "tentering") and then exposed in the Xenotest 1200.
  • the granules obtained are in a laboratory melt spinning plant at a maximum temperature of 270 ° C and a speed of 600 m / min a 12.1 decitex multifilament. This is done with a Draw twister stretched and twisted. The aspect ratio is 1: 3.2, so that finally multifilaments of 3.9 decitex can be obtained. These multifilaments are mounted on white cardboard and then in the WEATHER-OMETER Ci 65 exposed.
  • 100 parts of polypropylene block copolymer powder are mixed with 0.05 parts of pentaerythrityl tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 0.10 parts of tris (2,4-di-tert -butylphenyl) phosphite, 0.1 part of Ca stearate and the stabilizers specified in Table 3 in the Brabender plastograph at 200 ° C. for 10 minutes. The mass obtained in this way is removed from the kneader as quickly as possible and pressed into a 2-3 mm thick plate in a toggle press.
  • Part of the raw compact obtained is cut out and pressed between two high-gloss hard aluminum foils with a hydraulic laboratory press for 6 minutes at 260 ° C. to a 0.5 mm thick foil, which is immediately cooled in a water-cooled press. Sections of 60 mm x 25 mm are now punched from this 0.5 mm film and exposed in a WEATHER-OMETER Ci 65 (black panel temperature 63 ⁇ 2 ° C, no irrigation). These test specimens are removed from the exposure apparatus at regular intervals and checked for their carbonyl content in an IR spectrophotometer. The increase in carbonyl absorbance during exposure is a measure of the photooxidative degradation of the polymer and is known from experience to be associated with a decrease in the mechanical properties.
  • octadecyl-3- (3,5-di-tert- Homogenized butyl-4-hydroxyphenyl) propionate and the stabilizers given in Table 4 in a Brabender plastograph at 180 ° C for 10 minutes.
  • the mass obtained in this way is removed from the kn
  • Part of the green compact obtained is cut out and pressed between two high-gloss hard aluminum foils with a hydraulic laboratory press for 6 minutes at 170 ° C. to a 0.2 mm thick foil, which is immediately cooled in a water-cooled press. Sections of 60 mm x 25 mm are punched out of this 0.2 mm thick film and immersed in a 0.1 NH 2 SO 3 solution for 24 hours. This is considered a simulation of acid rain.

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Claims (20)

  1. Mélange synergétique de stabilisants contenant au moins deux composés polyalkylpipéridine choisis parmi les composants a), b), c) ou d), dans lequel
    le composant a) est au moins un composé de formule I
    Figure 00620001
    dans laquelle
    R1, R3, et R4
    représentent indépendamment les uns des autres un groupe alkyle en C1 à C12, cycloalkyle en C5 à C12, cycloalkyle en C5 à C12 substitué par un groupe alkyle en C1 à C4, phényle, phényle substitué par un groupe -OH et/ou alkyle en C1 à C10, phénylalkyle en C7 à C9, phénylalkyle en C7 à C9 substitué sur le groupe phényle par un groupe -OH et/ou alkyle en C1 à C10 ou un groupe de formule II
    Figure 00620002
    dans laquelle
    R5
    représente un atome d'hydrogène, un groupe alkyle en C1 à C8, O•, -CH2CN, alcényle en C3 à C6, phénylalkyle en C7 à C9, phénylalkyle en C7 à C9 substitué sur le groupe phényle par un groupe alkyle en C1 à C4 ou acyle en C1 à C8,
    et
    les groupes R1 et R3 représentent indépendamment les uns des autres un atome d'hydrogène,
    R2
    représente un groupe alkylène en en C2 à C18, cycloalkylène en C5 à C7 ou (alkylène en C1 à C4)di(cycloalkylène en C5 à C7)
    ou
    les groupes R1, R2, et R3 forment ensemble avec les atomes d'azote auxquels ils sont liés un système hétérocyclique de 5 à 10 chaínons,
    n1
    est un nombre allant de 2 à 50 et au moins un des groupes R1, R3, et R4 représente un groupe de formule II;
    le composant b) représente au moins un composé de formule III,
    Figure 00630001
    dans laquelle
    R6 et R8
    représentent indépendamment l'un de l'autre un atome d'hydrogène, un groupe alkyle en C1 à C12, cycloalkyle en C5 à C12, cycloalkyle en C5 à C12 substitué par un groupe alkyle en C1 à C4, phényle, phényle substitué par un groupe -OH et/ou alkyle en C1 à C10, phénylalkyle en C7 à C9, phénylalkyle en C7 à C9 substitué sur le groupe phényle par un groupe -OH et/ou alkyle en C1 à C10 ou un groupe de formule II,
    R7
    représente un groupe alkylène en en C2 à C18, cycloalkylène en C5 à C7 ou (alkylène en C1 à C4)di(cycloalkylène en C5 à C7)
    ou
    les groupes R6, R7, et R8 forment ensemble avec les atomes d'azote auxquels ils sont liés un système hétérocyclique de 5 à 10 chaínons,
    R9 et R10
    représentent indépendamment l'un de l'autre un groupe alkyle en C1 à C12, cycloalkyle en C5 à C12, cycloalkyle en C5 à C12 substitué par un groupe alkyle en C1 à C4, phényle, phényle substitué par un groupe -OH et/ou alkyle en C1 à C10, phénylalkyle en C7 à C9, phénylalkyle en C7 à C9 substitué sur le groupe phényle par un groupe -OH et/ou alkyle en C1 à C10 ou un groupe de formule II, ou
    R9 et R10 forment ensemble avec l'atome d'azote auquel ils sont liés un système hétérocyclique de 5 à 10 chaínons,
    n2
    est un nombre allant de 2 à 50 et au moins un des groupes R6, R8, R9 et R10 représente un groupe de formule (II);
    le composant c) représente un produit qu'on peut obtenir en mettant à réagir un produit, obtenu par la réaction d'une polyamine de formule IVa avec le chlorure d'acide cyanurique, avec un composé de formule VIb,
    Figure 00650001
    Figure 00650002
    formules dans lesquelles
    n3', n3" et n3'"
    représentent indépendamment les uns des autres un nombre de 2 à 12,
    R11
    représente un atome d'hydrogène, un groupe alkyle en C1 à C12, cycloalkyle en C5 à C12, phényle ou phénylalkyle en C7 à C9 et
    R12
    possède une des significations indiquées pour R5;
    le composant c) est au moins un composé des formules Va et Vb,
    Figure 00650003
    Figure 00650004
    dans lesquelles n4 et n4* représentent indépendamment l'un de l'autre un nombre de 2 à 50;
    avec la condition que (1) soient exclus le mélange de stabilisants contenant au moins un composé de formule I, au moins un composé de formule III et au moins un composé de formule VI,
    Figure 00660001
    dans laquelle R13 représente un atome d'hydrogène ou un groupe méthyle, R14 représente une simple liaison ou un groupe alkylène en C1 à C10 et n5 représente un nombre allant de 2 à 100, et (2) un mélange de stabilisants, qui contient en tant que deux composés polyalkylpipéridine différents seulement les composés exposés comme composant d) des formules (Va) et (Vb).
  2. Mélange de stabilisants selon la revendication 1, contenant au moins un composé appartenant au composant b) ou c) ou
    contenant au moins un composé choisi parmi les composants a), b) ou c) et au moins un composé appartenant au composant d) ou
    contenant au moins un composé appartenant au composant b) et au moins un composé appartenant au composant c) ou contenant qu moins deux composés appartenant au composant a).
  3. Mélange de stabilisants selon la revendication 1, dans lequel R5 représente un atome d'hydrogène, un groupe alkyle, en C1 à C4, allyle, benzyle ou acétyle.
  4. Mélange de stabilisants selon la revendication 1, dans lequel R5 est un atome d'hydrogène ou un groupe méthyle.
  5. Mélange de stabilisants selon la revendication 1, dans lequel
    R1, R3, et R4
    représentent indépendamment les uns des autres un groupe alkyle en C1 à C10, cycloalkyle en C5 à C7, cycloalkyle en C5 à C7 substitué par un groupe alkyle en C1 à C4, phényle, phényle substitué par un groupe -OH et/ou alkyle en C1 à C4, phénylalkyle en C7 à C9, phénylalkyle en C1 à C9 substitué sur le groupe phényle par un groupe -OH et/ou alkyle en C1 à C4 ou un groupe de formule II et
    R1 et R3
    représentent en outre, indépendamment l'un de l'autre, un atome d'hydrogène,
    R2
    représente un groupe alkylène en C2 à C10, cycloalkylène en C5 à C7 ou (alkylène en C1 à C4)di(cycloalkylène en C5 à C7)
    ou
    les groupes R1, R2, et R3 forment ensemble avec les atomes d'azote auxquels ils sont liés un système hétérocyclique de 5 à 7 chaínons,
    n1
    est un nombre allant de 2 à 40,
    R6 et R8
    représentent indépendamment l'un de l'autre un atome d'hydrogène, un groupe alkyle en C1 à C10, cycloalkyle en C5 à C7, cycloalkyle en C5 à C7 substitué par un groupe alkyle en C1 à C4, phényle, phényle substitué par un groupe -OH et/ou alkyle en C1 à C4, phénylalkyle en C7 à C9, phénylalkyle en C7 à C9 substitué sur le groupe phényle par un groupe -OH et/ou alkyle en C1 à C4 ou un groupe de formule II,
    R7
    représente un groupe alkylène en C2 à C10, cycloalkylène en C5 à C7 ou (alkylène en C1 à C4)di(cycloalkylène en C5 à C7)
    ou
    les groupes R6, R7, et R8 forment ensemble avec les atomes d'azote auxquels ils sont liés un système hétérocyclique de 5 à 7 chaínons,
    R9 et R10
    représentent indépendamment l'un de l'autre un groupe alkyle en C1 à C10, cycloalkyle en C5 à C7, cycloalkyle en C5 à C7 substitué par un groupe alkyle en C1 à C4, phényle, phényle substitué par un groupe -OH et/ou alkyle en C1 à C4, phénylalkyle en C7 à C9, phénylalkyle en C7 à C9 substitué sur le groupe phényle par un groupe -OH et/ou alkyle en C1 à C4 ou un groupe de formule II, ou
    R9 et R10 forment ensemble avec l'atome d'azote auquel ils sont liés un système hétérocyclique de 5 à 7 chaínons,
    n2
    est un nombre allant de 2 à 40;
    n4 et n4* sont indépendamment l'un de l'autre un nombre allant de 2 à 40.
  6. Mélange de stabilisants selon la revendication 1, dans lequel
    R1 et R3
    représentent indépendamment l'un de l'autre un atome d'hydrogène, un groupe alkyle en C1 à C8, cycloalkyle en C5 à C7, phényle, benzyle ou un groupe de formule II,
    R2
    représente un groupe alkylène en C2 à C8, cyclohexylène ou méthylèndi(cyclohexylène),
    R4
    représente un groupe alkyle en C1 à C10, cycloalkyle en C5 à C7, cycloalkyle en C5 à C7 substitué par un groupe alkyle en C1 à C4, et
    n1
    est un nombre allant de 2 à 25;
    R6 et R8
    représentent indépendamment l'un de l'autre un atome d'hydrogène, un groupe alkyle en C1 à C8, cycloalkyle en C5 à C7, phényle, benzyle ou un groupe de formule II,
    R7
    représente un groupe alkylène en C2 à C8, cyclohexylène ou méthylèndi-(cyclohexylène),
    R9 et R10
    représentent indépendamment l'un de l'autre un groupe alkyle en C1 à C8, cycloalkyle en C5 à C7, phényle, benzyle ou un groupe de formule II, ou
    R9 et R10 forment ensemble avec l'atome d'azote auquel ils sont liés un groupe 1-Pyrrolidyle, Pipéridino, Morpholino, 1-Pipérazinyle, 4-Méthyl-1-pipérazinyle, 1-Hexahydroazépinyle, 5,5,7-Triméthyl-1-homopipérazinyle ou 4,5,5,7-Tétraméthyl-1-homo-pipérazinyle et
    n2
    est un nombre allant de 2 à 25; et
    n4 et n4* sont indépendamment l'un de l'autre un nombre allant de 2 à 25.
  7. Mélange de stabilisants selon la revendication 1, dans lequel n1, n2, n4 et n4* représentent indépendamment les uns des autres un nombre de 2 à 20.
  8. Mélange de stabilisants selon la revendication 1, dans lequel
    R1 et R3
    représentent indépendamment l'un de l'autre un atome d'hydrogène, un groupe alkyle en C1 à C4 ou un groupe de formule II, dans laquelle
    R5
    est un atome d'hydrogène ou un groupe méthyle,
    R2
    représente un groupe alkylène en C2 à C6,
    R4
    représente un groupe alkyle en C1 à C10 ou cyclohexyle et
    n1
    représente un nombre allant de 2 à 20;
    R6 et R8
    représentent indépendamment l'un de l'autre un atome d'hydrogène, un groupe alkyle en C1 à C4 ou un groupe de formule II, dans laquelle
    R5
    est un atome d'hydrogène ou un groupe méthyle,
    R7
    est un groupe alkylène en C2 à C6,
    R9 et R10
    sont indépendamment l'un de l'autre un groupe alkyle en C1 à C8 ou un groupe de formule II,
    dans laquelle R5 a la signification ci-dessus indiquée, ou
    R9 et R10 forment ensemble avec l'atome d'azote auquel ils sont liés un groupe Morpholino et
    n2
    représente un nombre allant de 2 à 20; et
    n4 et n4* sont indépendamment l'un de l'autre un nombre allant de 2 à 20.
  9. Mélange de stabilisants selon la revendication 1, dans lequel le composé de formule I est
    Figure 00710001
    ou
    Figure 00710002
    et le composé de formule III représente
    Figure 00710003
    et
    n1, n2, n4 et n1* représentent indépendamment les uns des autres un nombre de 2 à 20.
  10. Mélange de stabilisants selon la revendication 1, contenant les composés
    Figure 00720001
    et
    Figure 00720002
    formules dans lesquelles n1 et n2 représentent un nombre de 2 à 20.
  11. Mélange de stabilisants selon la revendication 1, dans lequel n3', n3" et n3'" représentent indépendamment les uns des autres un nombre de 2 à 4, R11 représente un groupe alkyle en C1 à C4 et R12 représente un atome d'hydrogène.
  12. Mélange de stabilisants selon la revendication 1, dans lequel le composant c) représente un produit qu'on peut obtenir en mettant à réagir un produit, obtenu par la réaction d'une polyamine de formule
    Figure 00720003
    avec le chlorure d'acide cyanurique, avec un composé de formule
    Figure 00730001
  13. Mélange de stabilisants selon la revendication 1, contenant le composé
    Figure 00730002
    dans lequel n1 est un nombre de 2 à 20, et
    un produit qu'on peut obtenir en mettant à réagir un produit, obtenu par réaction d'une polyamine de formule
    Figure 00730003
    avec le chlorure d'acide cyanurique, avec un composé de formule
    Figure 00730004
  14. Mélange de stabilisants selon la revendication 1, contenant un mélange des composés Va et Vb, dans lequel n4 et n4* sont indépendamment l'un de l'autre un nombre de 2 à 20, et le composé
    Figure 00740001
    ou
    Figure 00740002
    dans lequel n1 et n2 représentent indépendamment l'un de l'autre un nombre de 2 à 20,
  15. Mélange de stabilisants selon la revendication 1, contenant un mélange des composés Va et Vb, dans lequel
    n4 et n4* représentent indépendamment l'un de l'autre un nombre de 2 à 20, et
    un produit qu'on peut obtenir en mettant à réagir un produit, obtenu par réaction d'une polyamine de formule
    Figure 00740003
    avec le chlorure d'acide cyanurique, avec un composé de formule
    Figure 00740004
    et
  16. Mélange de stabilisants selon la revendication 1, contenant le composé
    Figure 00750001
    dans lequel n2 est un nombre de 2 à 20, et un produit qu'on peut obtenir en mettant à réagir un produit, obtenu par réaction d'une polyamine de formule
    Figure 00750002
    avec le chlorure d'acide cyanurique, avec un composé de formule
    Figure 00750003
  17. Composition contenant un matériau organique sensible à la dégradation par oxydation, thermique ou induite par la lumière et un mélange de stabilisants selon la revendication 1.
  18. Composition selon la revendication 17, dans laquelle le matériau organique est une polyoléfine.
  19. Composition selon la revendication 17, dans laquelle le matériau organique est le polyéthylène, le polypropylène ou un copolymère de polyéthylène ou de polypropylène.
  20. Utilisation d'un mélange de stabilisants selon la revendication 1 pour stabiliser un matériau organique sensible à la dégradation par oxydation, thermique ou induite par la lumière.
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EP0757075A2 (fr) * 1995-07-31 1997-02-05 Sumitomo Chemical Company, Limited Composition de polyaminotriazine
GB2328210A (en) * 1997-08-14 1999-02-17 Clariant Gmbh Stabilizer mixture based on polyalkyl-1-oxazdiazaspirodecane compounds
EP0934972A2 (fr) * 1998-02-07 1999-08-11 Clariant GmbH Matières de moulage polyoléfiniques pour la production de feuilles /plaques calandrées
GB2341180A (en) * 1997-05-13 2000-03-08 Clariant Gmbh Compounds on the basis of polyalkyl-1-oxa diazaspirodecane compounds
EP0881222B1 (fr) * 1997-05-30 2004-01-14 Ciba SC Holding AG Procédé pour la préparation de polytriazines contenant des groupes 2,2,6,6-tétramethyl-4-piperidyl

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IL133922A (en) * 1999-02-01 2005-03-20 Ciba Sc Holding Ag Compositions comprising polyolefins produced by polymerization over a metallocene catalyst and a stabilizer mixture and a method for stabilizing said polyolefins
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IT1399477B1 (it) 2010-03-15 2013-04-19 3V Sigma Spa Miscele di ammine stericamente impedite per la stabilizzazione di polimeri
ITMI20110802A1 (it) 2011-05-10 2012-11-11 3V Sigma Spa Miscele di ammine stericamente impedite per la stabilizzazione di polimeri
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EP0709426A3 (fr) 1997-07-30
EP0709426A2 (fr) 1996-05-01

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